SU986299A3 - Method of producing 3-(phenyl)-spiro isobenzofuran-1(3n)-isoxazole-3-on or its derivatives - Google Patents

Abstract

3'-(Substituted phenyl)-spiro[isobenzofuran-1(3H),5'(4'H)-isoxazol]-3-ones have been found to be effective as herbicides and plant growth regulants, especially for the regulation of soybeans.

Description

39 tetrahydrofuran, chloroform, carbon tetrachloride, methylene chloride, dioxane and the like. Chloroximes are easily prepared by reacting hydroxylamine with the corresponding aromatic aldehyde in an aqueous alcohol, followed by chlorination of the irradiated oxime. Example 1o Preparation of 3- (3-b. Phenyl) -spiro1-isobenzofuran-1 (3N), a-isoxazole) -3-one. To a solution of α-biphenylyl carboxald hydrochloroxime (3.8 g, 0.15 mol) and 3-methylene phthalide (14.6 g; 0.1 mol) in 450 ml of ether, triethylamine is added dropwise at 5 ° C for 20 minutes. (15, 18 g, 0.15 mol.). The resulting mixture is stirred at room temperature for 20 hours. The solid is filtered. The ether solution contains very small amounts of the spiro compound, as shown by the results of NMR spectrum analysis. The solid, filtered from the original ethereal solution, extracted twice with 1200 ml of chloroform, chloroform solution twice water, dried over calcium sulphate, concentrated in vacuo to obtain 24.7 g (solid beige-colored product, ie, t / o). Recrystallization of 3.5 beige-colored solid from 100 ml of chloroform gives 1.4 / g of solid white color; mp, 170-172 0 with decomposition Found,%: C 77.36; H 4.45. about iJ Calculated,%: C 77.41; H 4.43. Example 2o Preparation 3- (4 -chlorophenyl) -spiro1. isobenzofuran-1 (3N), 5 () - isoxazole) -3-one, K solution 17.0 g (0.08 mol) para-chlorobenzaldehyde chloroxime and 14.0 (0.096 mol) 3-methylene phthalide in 300 ml of ether over one hour is added at 0-5 ° C 9 , 0 g (0.089 mol) of triethylamine in 50 ml of ether. The solution is allowed to react at room temperature for 20 hours. The IR spectrum of the sample indicates that the reaction has ended. The solid is filtered off. The ether solution is washed three times with a saturated aqueous solution of sodium chloride, dried over calcium sulfate and concentrated in vacuo. Only 2.0 g of crude product is obtained. The solid filtered from the initial solution is added to 500 ml of chloroform and washed three times with water. The chloroform solution remains cloudy even after the addition of 200 ml of tetrahydrofuran. The solution of tetrahydrofuran and chloroform is dried over calcium sulfate, filtered and concentrated in vacuo 10.2 g of a pale yellow solid are obtained (3,2%), ToPL. 158-1 ° C. A colorless solid with t „p„ Tbb-TbT C is obtained after several washes with ether. Found,%: C 64.14; H 3.37; N 4.67; CB 11.81. C N onNoseOz Calculated,%: C 64,12; H 3.3b; f / 4.67; From 11.83. EXAMPLE 3. Preparation of 3- (2-methylphenyl) -spiro (isobenzofuran-CZN), 5 (4H) -isoxazole-3-one. To a solution of ortho-tolualdehyde chloroxime (2b, 8 g; 0.158 mol), 3 methylene phthalide (14.6 g; 0.7 mol) and ether 4400 ml) was added dropwise a solution of triethylamine (16.0 g; 0.158 mol) in 30 ml of ether for 45 minutes at 5-10 ° C. The mixture is stirred at room temperature for 40 hours and filtered. The collected solid was dissolved in 1 L of chloroform and 200 ml of water. Then the chloroform solution is washed twice with water, dried over calcium sulfate and concentrated in vacuo. 16.4 g of a white solid are obtained with a mp of “146149 ° C. The starting ethereal solution is washed twice with water, dried over calcium sulfate and concentrated to 100 ml. An additional 1.64 g of spiroderm is precipitated. The ether solution is further concentrated to 10.8 g of a yellow-brown oil, which does not contain significant quantities of the desired product. By recrystallization of 12.0 g of the crude spiro compound from a mixture of tetrahydrofuran and ether, 9.87 g of pure white solid are obtained, m.p. 159 164 ° С with decomposition. Found,%: C 73.06; H 4.74. Calculated,%: C 73.11 j H 4.69, Example 4, Preparation of 3- (3-cyanophenyl) -spiro (isobenzofuran-1 (3N), 5 (4H) -isoxazole) -3-one. A 3 (3-cyanophenyl) -spiro (isobenzofura-1 (3N), 5 (4H) -isoxazole) -3-bh is prepared according to example 3 with the selected OUTPUT 62.7. The resulting spiro-coupling is a white solid with m, pl. . By recrystallization of 12 g of the crude spiro compound from a mixture of tetrahydrofuran and toluene, SjijS of a white solid is obtained with a mp. 1b5-1b7 ° C. Found,% C 70.07; H 3.50; Calculated,%: C 70, H 3.67. Example 5. Getting C-C-trifluoromethylphenyl) -spiro (isobenzofuran- 1 (3N), 5 () -isoxazole) -3-one 3- (trifluoromethylphenyl) -spiro (isobenzofuran-1 (3H), 5 (V H) -isoxazole) -3-one is obtained analogously to Example 3 with a yield of 36.8%. Recrystallization 5.0 g of the crude product from 75 ml of tetrahydrofuran and 50 ml of ether gives 3.83 g of pure substance in the form of white crystals with m. square 177-178 C, Found,%: C 61.29; H 3.06 L Oz Calculated,%. C, 61.27; H 3.02. Example 6, Preparation of 3 (.2-trifluoromethylphenyl) -spiro (isobenzofuran-1 (3N), 5W H-isoxazole-3-one 3- (2-trift-6-methylphenyl espiro (isobenzofuran-izn), 5 (H = isoxazole) -3- it is prepared according to Example 3 with an output of 35.2%. The crude spiro compound obtained in this way (Represents so (break solid white substance with T.1). By recrystallization 5 g of this substance from tetrahydrofuran (50. ml) and ether (50 ml), 12 g of colorless needles are obtained, mp: 156-157 ° C. Found: C 61, H 3.05 TsN pR MOZ Calculated,%: C 61.27; H 3.05. Example 7 The preparation of 3- (3-m hydroxyphenyl) -spiro (isobenzbfuran-1 (3N 5 (AH) -isoxazole) -3-one, 3 (Z-methoxyphenyl) -spiro (iZobenzofuran-1 (3N), 5 (H) -isoxazrel) was prepared as in Example 3. The starting ethereal solution was washed twice with water, dried over CaSO4, and concentrated to 29.6 g of a thick oil. contains 50 spiro compounds determined by NMR spectroscopy. The solid filtered from the initial ethereal solution gives 5.56 g after treatment (yield 18.8% of the desired product as a yellow solid with ToPL. 119123 ° C. By recrystallizing the solid from a mixture of tetrahydrofuran and ether, 4.3 g of a pale yellow solid are obtained, mp. 12 -12bs with decomposition. Found,%: C 69.03; H i |, SO. Calculated% C 69.15; H | ,. Example 8. Getting 3 - (3-phenoxyphenyl) -spiro (isobenzofuran1 (3N), 5 (a) - isoxazole) -3-one. 3 -13-phenoxyphenyl) -spiro (isobenzofuran-1 (3N), 5 (H / -isoxazole) -3-one) is obtained with a yield of 53.9% according to the method described in Example 3. The crude product is a yellow oil. Purification of 7.9 g of this oil by high pressure liquid chromatography on silica gel with a mixture of 50% ethyl acetate and 50% hexane gives, as the mobile phase, 2 g of the desired product as a white solid, mp 1-116 C. Example 9. Obtaining 3- (3-chlorophenyl) -spiro (isobenzofuran-1 ZN), 5-isoxazole) 3- (Z-chlorophenyl) -spiro (isobenzofuran-1 (ZN), 5 1 n) -isoxazole) -3-one is obtained with 86, |% yield according to Example 3. The crude product was a gummy veschestvoiPerekristallizatsiey, 19 g of the adhesive mixture of tetrahydrofuran and ether to give 5.2 g solid, m.p. 119,125 ° C. A weighed portion of 3.5 g of the solid is further purified by high pressure liquid chromatography on a column of silica gel with 50% hexane and 50% ethyl acetate as the mobile phase and 1.77 g of the desired product are obtained as a white solid, m.p. 127-129 ° C. Found:%: 63.88; H 3, "0 TschCH" "C Calculated,%: C 6, T2; H 3.36. Example 10. Preparation of 3- (21, -dichlorophenyl.) -Spirr (isobenzofuran-iZN), 5 × HH) -isoxazole) -3 one. Reaction 2, "- dichlorobenzaldehyde chloroxime and 3-methylenephthalide wire-. d by a method similar to that described in example 2. The solid collected from the reaction mixture constitutes 12.2 g of the desired product after treatment, and the ether solution yields k g of the desired product (70.2% yield). Recrystallization from chloroform results in X purification of white crystals, m.p. target product. Found,%: C: .57.63; H 2,1k, “, Calculated,% С, 57.86; H 2.73. Example P. Preparation of 3-phenylspiro (isobenzofuran -1 (3N), 5 C H) -isoxazole 7-3 She. 3 Phenylspiro (isobenzofuran-1 (3H 5 (4H) -isoxol-3 it is obtained by the method described in example 2, with 30 output). Hopp, C, Found,%: C 72.39; H ij, 2K b Calculated ,%: C, 72.5; H, 4.18. EXAMPLE 12 Preparation of 3 - (3-trifluoromethylphenyl-spiro (isobenzofuran-1 (3N), 5 (H) -isoxazole-3-one. K a solution of 109.5 g (0.75 mol) of 3-methylene phthalide and 285 g (1.27 mol) of meta-trifluoromethylbenzaldehyde chlorox in 3.5 liters of ether was added to 128.3 g of triethylamine in 250 ml of ether at 0 ° C. for 3 hours. "Then the solution is left under stirring overnight. The IR spectrum shows when the reaction is over. Solid The solution is filtered. The ether solution is washed once with 10% hydrochloric acid and twice with saturated aqueous sodium chloride solution, dried over calcium sulphate and concentrated in vacuo. Only 1.9.5 g of the crude product is obtained. from the original reaction solution, stirred with t l of tetrahydrofuran for 4 h and filtered through a Buchner funnel. The resulting tetrahydrofuran solution is washed once with a solution of hydrochloric acid and twice with a saturated aqueous solution of sodium chloride. After drying and concentrating, a solution of tetrahydrofuran gives 140.6 pure product, m.p. 170 ° C, ... Found,%: C 61.25; H 3.04. Calculated,%: C 61.2b; H 3.02. Example 13 Preparation of z- (pa jpa-fluorophenyl-cPyro isobenzofuran-U3H-5H4n; -isoxazole-, 3-one. 3- (para-fluorophenyl) spyro (isobenzofuran-1 (3H), 5 (4H; -isoxazole ; .- 3on is obtained by the method described in Example 1, with the output. T, pLo 142-145 ° C. Found,%: C 67.89; H 3.59 .. t H jjFNOj Calculated,%: C 67, 84; H 3.56, 998 The compounds of the formula I can be used as such or as an active ingredient of the herbicidal composition. In the present usage, the term herbicidally active ingredient is understood as a compound of the formula I. The regulation of the growth of undesirable weeds can be achieved by attaching a herbicidally active ingredient to a plant locus, which in the present definition includes a growth medium, a surrounding plant, seeds, seedlings, roots, stems, leaves, flowers, and other parts of the plant. To show the herbicidal properties of the compound of formula I, They are tested as follows: A high quality soil layer is placed in aluminum baths and compacted to a depth of 0.35-2.27 cm from the top edge of the trays. A predetermined number of seeds or employees for breeding growth shoots of plants of various species that are placed at the level of the soil are placed on the soil surface. The baths are filled with soil after the sowing or planting of the growth shoots. A known amount of herbicide active ingredient in the form of a solution or wetted -. The crushed powder is introduced into the soil, mixed thoroughly and used as a covering layer for the prepared baths. After the treatment, the baths are placed in a tile and moistened from below to evenly distribute the moisture necessary for germination and development of the plants. Approximately 2-4 weeks after sowing and processing, the plants are inspected to determine all deviations from normal growing conditions and the results are recorded. To assess the degree of phytotoxicity of each species, a herbicidal evaluation code is used. Estimates are determined as follows: Regulation,% Grade 0-24О 25-491 50-742 75-1003 The plant species used in these tests are designated by the letters: A baud g field; 8 - cockcock; G Limnokharis; Dg-ipome; K - chicken millet; L g dream kulturna; M - sugar beet; N is wheat; E - mary

bel; F - water pepper; G - yellow sedge; H - swine; 3 - Alep sorghum; J - pubescent fire; O - rice; P - sorghum; Q - wild buckwheat; R - Hemp Sesbania; S - millet; s T - millet African.

The results obtained during the pre-emergence tests; are presented in table. 1 and 2,

Post-emergence tests. About

Herbicidally active ingredients are applied in sprayed form on various plant species at the age of 2 or weeks. Splashes of a solution or suspension of a wettable powder, 5 containing the appropriate proportion of herbicidally active ingredient to achieve the desired evaluation of the test, and a surfactant are applied to the plants. The treated plants are placed in the greenhouse and after about two or four weeks the effect of the herbicide is observed.

The test results are presented in Tables 3 and i, in which the post-emergence-Z5 new herbicidal evaluation code looks as follows:

Regulation,% Evaluation

Q-2kО

 thirty

75-993

100k

The plant species used in these tests are indicated by letters, the value of which remains the same,

The above tables show that the use of compounds of formula 1 leads to destructiveness. damage to undesired paic-o weeds In addition, the use of silyo compounds of formula I is possible to control the growth of desirable plants, especially legumes, such as those with the S cultured. Found that compounds of formula I are effective as growth substances for a plant of the legume family.

The term regulation of jg growth or plant development should be understood as a modification of the normal subsequent development of the treated desired plants to their own maturity. Such modifications are most often observed as changes in the size, shape, color or structure of the treated plant or its parts. Similar to this for visual inspection.

changes in the amount of plant fruit or flowers are also quite obvious. The above-mentioned changes can be characterized as accelerating or slowing down plant growth, reducing size, changing leaves or crown, increased branching, inhibition of apical shoots, enhanced flowering, both; zlystvenie, enhanced growth of 1 root, increased frost resistance, etc.

When using the spiro compounds of formula 1 as the active ingredient of the plant growth regulating composition, it is clear that these compounds have growth regulating activity, which are tested by the following method.

A certain number of soybean cultivars Wi EEVans are grown from seeds in plastic pots in a greenhouse for one week, after which the plants are laid out one by one per pot. When the second trefoil is complete (Dissolves (three weeks), the plants are treated with a solution of the active ingredient in acetone and water. Aqueous Tween 20 (polyoxyethylene sorbitan monolaurate) is used as a surfactant)

When the fifth week trefoil is fully developed, the plants formed are compared with untreated control plants and the observations are recorded.

The results of the observations are summarized in table. five.

As can be seen from the cited data, the proposed spiro compounds are particularly effective for reducing the size of soybean plants, as well as changing the foliage morphology. The data indicate that the compounds can be used as herbicides or as plant growth regulators. If they are used as herbicides, then it is desirable to use them in doses of 1.12, 2 kg / ha. Doses of from 2 k / ha are particularly preferred.

It is recognized that more than 11.2 kg / ha can be used for reasons of economy and efficient use of equipment, the degree of application is higher than 11.2 kg / ha when the proposed compounds are used to regulate the growth of leguminous plants, such as soybean culture. The degree of use can be 0-, 05b-5.6 kg / ha, preferably 0.056-2.8 kg / ha. When choosing the appropriate time and dose of application of the active ingredient, it should be assumed that the exact amounts also depend on the desired response, method of application, plant species, soil conditions and various other factors. To achieve the desired effect, single and multiple applications of the active ingredient can be used. ingredient. The active ingredient used as a herbicide or as a plant growth regulator can be used alone or in combination with other pesticides or materials known as auxiliary, as a liquid or in solid form. To prepare such compositions, the active ingredient is mixed with an auxiliary material including diluents , fillers, carriers and modifying agents to form compositions in the form of fine solid particles, granules, pellets, wettable powders, dust, solutions and aqueous dispersions s or emulsions. Thus, the active ingredient can be used with an auxiliary material, such as fine particles of a solid, liquid organic solvent water, a wetting agent, dispersing sludge emulsifying agents, or any suitable combination of the listed ingredients. Suitable finely dispersed solid carriers and fillers used in 8 compositions include talc, glycine, pumice, silica, diatomaceous earth, quartz, fuller's ze (1yu, sulfur, powdered cork and wood, peanut flour, chalk, lime , tobacco dust, charcoal, etc. Liquid diluents include Stoddard solvent, acetone, alcohols, glycols, ethyl acetate, benzene, etc. Growth regulating compounds, in particular liquids and wettable powders, usually contain one or more surfactant substance in to sufficient to give the compositions rapid wettability in water or in oil. Typically, the active ingredients are used in the form of compositions containing one or more auxiliary components, the introduction of which provides for the use of uniform distribution of the active ingredient. in the form of liquids or particles (. solids) can be carried out by conventional means using, for example, sprinklers, dust sprays, hand and sheath x nebulizers, and sprayers pollinator. The compositions may also be sprayed or sprayed from an airplane. The proposed formulations, regardless of whether they are used as herbicides or plant growth regulators, usually contain 5-95 hours. active ingredient, 1-50 weight. Cho surfactant, substances and -9 weight.h. solvent, all weight parts being taken relative to the total weight. Table 1

2 3

i

6

15

986299

16 Continued table. 2

17

986299

.18 Table 3

The price is 11.2 kg / ha.

Ta b lm 4 k

Species (throwing

J3 2.8 0.5b 0.112 2.8 0.56 0.112 3.8 0.5b 0.112 2.8 0.56 0.112 2.8

986299

20 table

Table 5 Reduction in size, changes in young and old leaves, oppression of leaves and buds in the sinuses, decrease in dry weight The same - V Reduction in size, dark coloring of leaves, oppression of leaves, deformation of young and old leaves, decrease in dry weight Same Reduction in size, change in cover , leaf depression, change of old and young leaves, decrease of dry weight, weight Same Change of old and young leaves, decrease of dry weight, decrease of dry weight, decrease in size, oppression, development of the apex, leaf depression, change, ov of developing leaves, curvature of .baths in the lower part, decrease in dry weight. Reduction in size, inhibition of apical shoots, inhibition of leaves, change in newly developing leaves, epinasti, decrease in dry weight. The same reduction in size, inhibition of leaves, deformation of old and young leaves, epinasti. , decrease in dry weight 0.56 0.112 2.8 0.5b 0.112 2.8 0.56 0.112 2.8 0.5b 0.112 2.8 0.5b 0.112 2.8 0.5b 0.112 Size reduction, modified cover, deformation young and old / fHcTbes, epinasti, dry weight reduction. Decrease in size, deformed cover, altered old and young leaves, epinasti, decrease in dry weight Decrease in size, deformation of old and young leaves, epinasti, decrease in dry weight Decrease in size, deformation of young and old leaves, dark coloring of leaves, oppression of leaves, decrease dry weight Decrease in size, deformation of old and young leaves, leaf depression, decrease in dry weight Decrease in size, growth inhibition of the top, dark leaf color, often leaf structure, leaf oppression, decrease dry weight Decrease in size, inhibition of growth of the apex, dark color of leaves, inhibition of leaves, deformation of newly appearing leaves, decrease in dry weight Decrease in size, inhibition of development of the apex, inhibition of leaves, deformation of old and new leaves, decrease in dry weight Deformation old and young leaves, leaf depression, decrease in dry weight. Deformation of old and young leaves. No change is observed. Reduction in size, inhibition of the development of the apex, dark color of the leaves, part of the leaf structure, inhibition of the leaves. , Decreased dry weight, Size reduction, inhibition of progression apex, darken leaf coloring, portions of the sheet structure, inhibition of leaves, the dry weight -reduction Size reduction, inhibition of progression apex, dark color of leaves, leaf inhibition, deformation of young leaves, decreased dry weight. Leaf deformation, leaf depression Leaf deformation No change. ,,,

23

986299

2k Continued table. five

Claims (1)

Claim The method of obtaining 3 “(phenyl) -spirO (isobenzofuran-1 (3Н), 5 '(4'Н) -isox-'-zol) -3-one- or its derivatives of the formula where X and Y are independently hydrogen , chlorine or fluorine, methyl, methoxy, trifluoromethyl, phenoxy, _Λ phenyl or cyano, characterized in that the chloroxime of formula de X and Y have the indicated meanings and are reacted with 3-methyl-Lenphthalide in the presence of triethylamine at 0-10 ° C in flow from 20 minutes to 3 hours and then at ambient temperature. Wednesday.